In aqueous solution, the micellization and microenvironment characteristics of the micelle assemblies of three anionic surfactants, sodium 1-(n-alkyl)naphthalene-4-sulfonates (SANS), have been investigated by steady-state fluorescence and time-resolved fluorescence decay techniques using pyrene, Ru(bpy)(3)(2+), and 1,6-diphenyl-1,3,5-hexatriene as fluorescence probes. The critical micelle concentrations (cmc's), effective carbon atom numbers (n(eff)'s), hydrophilic-lipophilic balances (HLBs), mean micelle aggregation numbers, micropolarities, and microviscosities of these surfactant micelles have been determined. The logarithmic cmc of the alkylnaphthalene sulfonates decreases linearly with an increase in the n(eff). The logarithmic aggregation number of the alkylnaphthalene sulfonates increases linearly with an increase in the n(eff). However, in contrast to the alkylsufonates and the alkylbenzene sulfonates, the aggregation for these alkylnaphthalene sulfonate molecules is less sensitive to the increase in the n(eff). The micropolarity of these alkylnaphthalene sulfonate micelles is less sensitive to the increase in the alkyl chain length and is lower than that of sodium dodecyl sulfate (SDS). The microviscosity of these alkylnaphthalene sulfonate micelles increases with an increase in the alkyl chain length and is lower than those of nonionic surfactants and zwitterionic surfactants. These results suggest that naphthyl rings have a notable effect on the micellization of SANS.